CN103547452B - Laser-engraveable flexographic printing precursors - Google Patents

Laser-engraveable flexographic printing precursors Download PDF

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Publication number
CN103547452B
CN103547452B CN201280024821.8A CN201280024821A CN103547452B CN 103547452 B CN103547452 B CN 103547452B CN 201280024821 A CN201280024821 A CN 201280024821A CN 103547452 B CN103547452 B CN 103547452B
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laser engraving
flexographic printing
layer
presoma
laser
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CN103547452A (en
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C.J.兰德里-科尔特雷恩
L.M.弗兰克林
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Eastman Kodak Co
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Eastman Kodak Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Plasma & Fusion (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)

Abstract

A laser-engravable flexographic printing precursor or other patternable material can be laser-engraved to provide a relief image. The relief image is formed in an elastomeric, relief-forming, laser-engravable layer comprising a thermoplastic elastomeric nanocrystalline polyolefin that is melt processable. The laser-engraveable composition can be readily recycled and reformed into another flexographic printing plate precursor.

Description

Can the flexographic printing presoma of laser engraving
Technical field
The present invention relates to can laser engraving flexographic printing presoma and comprise (patterable) material of the formed image being easy to recycled materials.Especially, these presomas and the material that can form image comprise can the layer of laser engraving, describedly the layer of laser engraving can comprise the nanocrystal polyolefin of the thermoplastic elastomer (TPE) with melt-processible, make the layer of laser engraving to be easy to melting and to be again formed as another presoma.The present invention also comprise matrix become flexographic printing component and the flexographic printing component used is recovered as new can the method for presoma of laser engraving.
Background technology
Flexographic printing plates (printing plate) is sometimes referred to as " relief printing plate (relief printing plate) " and have protruding matrix, and it on, applying ink is to be applied to printed material.Flexographic printing plates has elastomeric or elastomeric character usually.Make flexographic printing plates imaging in many ways.The commonsense method of described version imaging is the photosensitive composite exposure that will be coated in matrix by sheltering element (masking element) or the transparent body, then prepares matrix with the unexposed area of suitable solvent removing coating.Remaining exposure region can not be removed, because crosslinked these regions that make of photosensitive composite are insoluble to flushing (or development) solvent.These remaining areas provide the image-region the printing forming flexographic printing plates (working part) for the treatment of inking.Due to the crosslinked character of the gained of flexographic printing plates, it can not be easy to melting more again or dissolve and produce new flexographic printing plates presoma.The flexographic printing cylinder or seamless steel tube with required raised emboss picture can also be used to carry out flexographic printing.
Non-printing trap (non-printing well) in the embossment of flexographic printing plates is that at least 0.05 mm is dark in net area, and under the sight of thick flexographic printing plates or other flexographic printing component, the value of 3 mm at the most can be assumed to be in other imaging region.Therefore, lot of materials must be removed by laser.Therefore directly other technology of already having known from galley in fact in this respect of laser engraving is very different, wherein laser is only for imaging laminate, such as lithographic plate or the matte (mask) that is used on photopolymer flexographic plate, thus the actual production of flexographic printing plates is still subject to rinsing and the impact of developing method.
Existing various thermoplastic elastomer (TPE) described material and the adhesive that can in the layer of laser engraving be used as of ethylenic polymer in flexographic printing elements presoma.But this type of elastomer layer containing these thermoplastic elastomer (TPE)s needs usually by thermoplastic elastomer (TPE) and the heat combined by the chemically reactive substance forming crosslinked matrix or photochemistry being strengthened.
Containing can be used as between flexographic printing plates with the heat of 1,2-polybutadiene or the crosslinkable layer composition of photochemistry be described in EP 1,958, in 968 people such as () Nakamura and United States Patent (USP) 7,101,653 people such as () Kaczun.In these compositions, need to be cross-linked to provide good character.
It is generally known that can the layer of laser engraving should be cross-linked, harden or sulfuration to prevent the formation in laser ablation (imaging) period melted edge.Term " melted edge " refer to melting under the impact of the marginal layer of element carved at laser beam but not or fully do not decompose and discharge time, the material distortion formed during laser ablation or be out of shape.This is the Gaussian result formed with the limited radius of laser beam of the Space Thermal distribution of laser.Even if by washing subsequently, this melted edge can not be removed or at least can not fully remove, and they cause fuzzy printing.The unacceptable melting of described layer also causes the resolution ratio of printed patterns compared with numerical data record to reduce.
Such as, United States Patent (USP) 6,776, the block copolymer that 095 people such as () Telser describes use two step cross-linking method and various thermoplastic elastomer (TPE) provides can the flexographic printing plates presoma of laser engraving, and reduce during laser engraving step will the generation of melted edge of infringement printing performance.For realizing this, thermoplastic elastomer (TPE) can be the styrene-butadiene and styrene-isoprene block copolymer that combinationally use with suitable cross linking chemistries (crosslinking chemistry).
For preventing forming melted edge during laser ablation, United States Patent (USP) 7,290,487 (Hiller) describe crosslinkable, can the layer of laser engraving, it comprises the adhesive of hydmphobic elastomeric, plasticizer and cross linking chemistries.
Usually it is also known that can laser ablatable layer can also be crosslinked, sclerosis or sulfuration, with the ink during preventing by printing and the excess material that caused by version cleaning solvent swelling.
But, be that material that is crosslinked, sclerosis or sulfuration can not be easy to reprocess, again formed, re-use or be recycled to its initial composition and purposes easily by the problem that people are familiar with.Therefore, must abandon the flexographic printing plates used, this produces great environmental problem.
Although be useful for the crosslinked of significant reason elastic composition, but it also requires the composite-material formula containing crosslinked or sulfur vulcanization chemistries product, described composite-material formula causes manufacturing complexity and difficulty, such as early stage set (premature set-up), not exclusively solidification and short composition period of storage (being cross-linked in early days), particularly when forming relatively thick flexographic printing plates presoma.
Another problem is also met with containing when cinnamic polymer and copolymer when using.Containing in the cleaning solvent of acetic acid esters of printing (printing run) the ink deposition thing of period on clean flexographic printing plates, and in solvent based flexographic ink, these polymer have low solvent resistance and high swelling degree.This flexographic printing plates is swelling and distortion during printing, and causes lower printing quality.In addition, during printing, the solvent swell of flexographic printing plates damages the life-span of its resistance to abrasion, durability and version.
Therefore, in flexographic printing exist need technical staff solve some difficult problems, the method or the composition that solve one or more problem may worsen other problem.Also there is demand to the callable flexographic printing plates prepared by various not crosslinkable composition, described not crosslinkable composition is not got involved in various problem as above.
Summary of the invention
The invention provides can the flexographic printing presoma of laser engraving for what provide matrix, this presoma comprise at least one elastomeric, formed embossment, can the layer of laser engraving, described layer comprises thermoplastic elastomer (TPE) nanocrystal polyolefin.
In addition, the material that can form image comprises nanocrystal polyolefin and the radiation adsorber of thermoplastic elastomer (TPE).
In addition, the invention provides the method that matrix is provided in flexographic printing component by laser engraving, described method comprise by of the present invention can the flexographic printing presoma Imagewise exposure of laser engraving in laser engraving radiation to provide the component of the flexographic printing with matrix.
The present invention also provides the flexographic printing component with the matrix provided by laser engraving, and described flexographic printing component is included in the matrix in laser engraving layer, and described laser engraving layer comprises thermoplastic elastomer (TPE) nanocrystal polyolefin.
In addition, the method for flexographic printing of the present invention comprises: by of the present invention can the flexographic printing presoma Imagewise exposure of laser engraving in laser engraving radiation to obtain the flexographic printing component with matrix, and
Use described flexographic printing component in flexographic printing.
For the system of laser engraving flexographic printing plates presoma, to form flexographic printing component, described system comprises:
Can the flexographic printing presoma of laser engraving for what provide matrix, this presoma comprise at least one elastomeric, formed embossment, can the layer of laser engraving, described layer comprises the nanocrystal polyolefin of thermoplastic elastomer (TPE), and
One or more laser engraving radiation source, its be directed to provide described can the laser engraving of layer of laser engraving.
Of the present inventionly the flexographic printing presoma of laser engraving can be easy to imaging to be provided for the matrix of flexographic printing.These presomas comprise formed embossment, can the layer of laser engraving, described layer comprises the adhesive being easy to the uniqueness reclaimed.The adhesive of this uniqueness makes this presoma can laser engraving, and does not form image defects (such as melted edge).In addition, this unique adhesive provides the very important physical property of flexographic printing plates, particularly, be good elasticity and compression reaction, and before and after printing in the solvent of clean described version and low swelling what be usually used in the solvent in solvent based ink formula.The adhesive of these advantages is provided to be thermoplastic elastomer (TPE) nanocrystal polyolefin (as to give a definition).
Accompanying drawing is sketched
Fig. 1 is G ' as described in Examples below and G " diagram of modulus (moduli) Relative Oscillation frequency.
Detailed Description Of The Invention
Definition
Determine that to give a definition various term used in the disclosure and term are to define the present invention.Unless otherwise indicated, these definition are intended to get rid of other definition that term or term may exist in the prior art.
Term " thermoplastic elastomer (TPE) " or TPE refer to the polymer (homopolymers or copolymer) showing both thermoplasticity and elastomer character.Although most of elastomer is thermosets, thermoplastic elastomer (TPE) shows rubber elasticity at ambient temperature, and is fluidized by heating and is therefore relatively easy use in processing (such as injection moulding and extrude).Main Differences between thermo-setting elastomer and thermoplastic elastomer (TPE) is the type of the cross-bond in their structures.Crosslinked in thermosetting polymer is the covalent bond generated by chemical reaction.On the other hand, crosslinked in thermoplastic elastomer (TPE) is generated by physical association, described physical association occur in one of this material mutually in and be called as physical crosslinking.Such as this physical association can be ruptured by heating, and again will be formed when cooling.Therefore it is reversible.
Term " chemical crosslinking " refers to the situation that chemical bond that the composition when composition is produced by chemical reaction is crosslinked.Chemical crosslinking (herein referred to as " being cross-linked ") is a key polymer chain being connected to another.Chemical crosslinking relates to and being bonded together by two or more polymer molecule with strong chemistry or covalent bond.Chemical crosslinking causes molecular weight to increase sharply and the corresponding increase of melt viscosity.These crosslinked differences of facilitating the physical property of polymeric material.Say polymer " is cross-linked " time, the entirety of this polymer is normally exposed to cross-linking method by.Mechanical depends on crosslinked amount or crosslink density consumingly with the change of rheol character gained.When the degree of cross linking is low, the described crosslinked structure causing formed polymer to have higher molecular weight or even cladodification.Lower crosslink density increases the viscosity of polymer melt, but does not cause the stopping completely of smelt flow character.When crosslinked amount increases further, a part for polymer will form polymer network, and it does not dissolve and only swelling in a solvent.This also cause completely with the formation of unlimited polymer network (also referred to as gel)." gel point " of the gelatification in polymer chemistry or critical point are the points that unlimited polymer network occurs first.When approach to criticality point (gel/infinite network is formed), disperse viscosity logarithm.In the case, under the effect of mechanical stress applying Infinite Time, gel will not flow.Therefore, thus crosslinked polymer loses its thermoplastic properties and no longer melt-processable.This makes melt-processed equipment (such as extruder, Coinjection molding apparatus and calender device) not be suitable for these materials of processing.
Chemical crosslinking can be formed by the chemical reaction caused by heat, pressure, pH change or radiation.Such as, by the unpolymerized or partially polymerized resin containing reactive functionality be called that the specified chemical goods of crosslinking agent mix and form crosslinked chemical reaction to produce.Also can cause crosslinked by being exposed to radiation source (such as electron beam, γ radiation or ultraviolet light) in normally thermoplastic material.Described cross-linking reaction can be that heat is brought out, such as in the formation of thermo-setting elastomer (such as urethanes or epoxy resin), or in the reaction of the compound (such as acrylate) containing multiple ethylenic unsaturated group, or in the sulfuration of rubber using sulfur-bearing or peroxide firming agent, or it can be photochemically induced, such as in the reaction of the acrylate containing multiple ethylenic unsaturated group, or by reaction that free radical causes.The chemical process of sulfuration is a kind of crosslinked, and that it changes the character of rubber.The method is commonly referred to sulfur curable (sulfur curing) but peroxide also can be used to realize.Crosslinked is the characteristic of thermosets.Chemical covalent is crosslinked once be formed, and is mechanically stable and heat-staple, chemical covalent is crosslinked be difficult to destroyed.In general, chemical crosslinking is irreversible, and if heating, the thermosets of gained will be degraded or burn and can not melting.Once polymer is by chemical crosslinking, then product is difficult to or can not melting and recovery.Necessarily reclaim raw material with specified chemical process and program.
Chemical crosslinking needs to use crosslinking agent usually, (acid-generating) initator of such as catalyst free radical or product acid, light trigger, or these combination.Crosslinking agent is such material, its promote or telomerized polymer chain between covalent intermolecular bond, they are joined together to form more rigid structure.Therefore, in general, the version not having chemical crosslinking will not be produced containing the precursor composition of chemical cross-linking agent with the combinations of substances that can be crosslinked.In addition, will not photosensitive containing the precursor composition of chemical cross-linking agent thus be subject to photochemical crosslinking impact.
But, likely, can the flexographic printing presoma of laser engraving really containing the chemical crosslinking that produced by the reaction of chemical cross-linking agent, but these chemical cross-linking agents are totally consumed during chemical reaction He before preparing presoma, and wherein these are cross-linked the smelt flow character not hindering material.In some such cases, crosslinked that only may relate to the interior separation of material, discontinuous or disconnected region, wherein the entirety of this material or the continuous phase of this material keep noncrosslinking.In another example, inclusion (such as previously crosslinked particle or globule) is added in noncrosslinking material.These particles or globule can be organic or inorganic materials.In these cases, as long as the inclusion of these precrosslink is not reacted with the continuous phase of material further, then overall viscosity can not be increased to infinity, and maintenance is melt-processable by this material.
In material, the existence of gel like structure can by rheology and viscoelasticity measurement.In processing equipment (such as blender, grinding machine, calender, extruder and blow moulding equipment), the behavior of noncrosslinking rubber like polymer is maintain close ties with the viscoelasticity property of the material of domination smelt flow behavior.[J. D. Ferry writes for " Viscoelastic Properties of Polymers ", the third edition; John Wiley & Sons, Inc., NY, 1980.] under frequency of oscillation under periodicity small deformation, by measuring viscoplasticity behavior, the change of the physical property that monitoring is crosslinked, such as, use mechanical spectrometer to measure.Method for the viscoelasticity property measuring theme resin (subject resin) relate to use under frequency of oscillation in a periodic manner instrument (be such as equipped with vibration parallel-plate flow graph mechanical spectrometer) make disc sample bear minimum distortion (being less than the strain of 1%).During sample deformations, lose a certain amount of energy due to molecule segment motion.Dump energy is stored by elastic mechanism.Measure this two class behavior at test period simultaneously and be reflected in the size of loss modulus (G ") and storage or modulus of elasticity (G ').Use frequency sweep to study the time dependence shear behavior of these viscoelastic properties, and carry out vibration test under frequency conversion, and amplitude reserving and temperature are steady state value.Measurement should be carried out more than " the association temperature of associating/go " of the fusing point of any crystal region or any " physical crosslinking ".Frequency sweep can be used clearly to distinguish crosslinked with noncrosslinking material, as at " The Rheology Handbook ", the second edition, Thomas G. Mezger writes, publisher: Vincentz Network GmbH & Co., Hannover, Germany, describe in the chapter 8 of 2006.For noncrosslinking polymer, when drawing logarithmically, G ' and G " modulus reduces continuously with the reduction (in low frequency, or in stub area) of frequency of oscillation.Therefore, these noncrosslinking materials show smelt flow behavior.For crosslinked polymer, G ' modulus curve and G " modulus curve approaches almost constant, frequency independently limiting value, and it has the slope close to zero.Crosslinked polymer does not show the flow behavior of fused mass.
Term " physical crosslinking " refers to have and form the cancellated physical crosslinking of physics to realize the thermoplastic elastomer (TPE) (TPE) of stability in polymer micro-structural.About molecular structure, TPE comprises the soft segment phase of the glass transition temperature had lower than serviceability temperature, and prevents the hard segment of the plastic deformation near environment temperature or serviceability temperature.The example of described hard segment includes but not limited to that glass transition temperature is higher than the phase of serviceability temperature, crystalline phase, hydrogen bond or Ion Phase.They describedly firmly provide usually reversible physical crosslinking or physical network structure mutually, so can such as control to be formed and again formed by hot-working." association temperature of associating/go " is defined as material from the temperature having physical crosslinking or netted structure and become the material of above-mentioned noncrosslinking material flowing and behavior.
In the context of thermoplastic elastomer (TPE), term " melt-processable " refers to higher than under fusion temperature or association/go association temperature, the material that can show smelt flow behavior as hereinbefore defined.Therefore, non-melt is processed by the material (as hereinbefore defined) of chemical crosslinking.
Term " nanocrystal " refers to the material of diameter in the grain size number of nanometer range (being less than a micron).
Typically, semi-crystalline polymer will have the form that wherein domain is dispersed into " island (sea-island) " state, and wherein amorphous domain is " sea " and crystalline region is " island ".In the polyolefinic situation of nanocrystal, morphosis is such, wherein " island " has diameter and is less than 1 μm and the crystalline volume of general 10 nm (nanometer) to 400 nm, and they communicate with each other to form network structure, thus equably across whole amorphous domain.Such as and not exclusively, this can be realized by synthetic segmented copolymer, wherein adjacent block has different steric regularities (such as isotaxy and atactic) and therefore has different crystallization behaviors.Therefore, such as, the segment of the island of the isotactic block of crystallization via the atactic block of monomeric substance is connected.Alternatively, can construct the block derived from different monomeric substances, wherein a kind of monomeric substance will form amorphous phase by forming the monomeric substance of crystalline phase with other.Because this physical network structure, the nanocrystal polyolefin used in the present invention has IMAGE, heat resistance and pliability.Although the elastomer outside the present invention has roughly micron or larger grain size number, but there is controlled grain size number as implied above for putting into practice thermoplastic elastomers of the present invention, to provide the elasticity needed for flexographic printing component and the combination for the very important high thermal distoftion temperature of laser engraving.TPE of the present invention has both nano junction crystalline region and amorphous region, this provides the elasticity needed for flexographic printing plates and compression reaction.
The size of crystallized domains or crystal region or grain size number should not obscured with crystallite size.Without domain size, the crystallite that crystallized domains or district are generally about 50-250 dust by many sizes forms.The size of crystallite is generally measured by X-ray diffraction.The size in crystallized domains or district can be passed through methods known in the art (such as transmission electron microscopy) and measure under magnification at high multiple.
In practice, by between the polarizer that the film of material is placed on two relative to each other rotated ninety degrees angles (namely, by cross-polarized light device) and use microscopic examination transmitted light, can determine whether non-oriented crystalline material has the crystalline texture being greater than the roughly wavelength of visible ray with wherein grain size number and form the nanocrystalline structures contrasted.When non-polarized light is by plane polariscope (polariscope eyeglass) transmission, it becomes plane polarization in one direction.If make the light of polarization another plane polariscope subsequently by first being 90 degree of orientations, then will without Transmission light.
Polarised light and anisotropic material interact.This sees in crystalline material usually.Because in these materials, refractive index is different for the polarised light of horizontal and vertical, so the polarizability of anisotropic material is unequal in all directions.This anisotropy causes the change of the polarization of incident beam, and can easily observe with cross-polarized microscopy or polarimetry.In such cases, time between the polarizer anisotropic or crystalline material being placed on 90 degree of orientations each other, light is by transmission.Isotropic material (such as non-oriented amorphous polymer) does not interact with polarised light, and therefore, time between the polarizer that this material is placed on 90 degree of orientations each other, light is by not transmission.
Be less than the wavelength of visible ray and the nanocrystalline domains of random orientation or district by cross-polarized light device assembly by unpolarized for not transmission visible ray.When the size of crystallized domains becomes enough large and is considered as " non-nano crystallization " definition of " nanocrystal " stated herein (mean outside), light will be transmitted through orthogonal polarizer assembly.
Term " flexographic printing presoma " refers to goods of the present invention or element, and it may be used for preparing flexographic printing component of the present invention and can be the form of flexographic printing plates presoma, flexographic printing cylinder presoma or flexographic printing elements presoma.
Term " flexographic printing component " refers to goods of the present invention, it is the flexographic printing presoma of imaging and can is the form of the galley with the elastomeric outmost surface being substantially plane, has the printing cylinder of bending elastomer upper space or the form of seamless printing sleeve.Flexographic printing component has matrix (that is, the layer of laser engraving) in outmost surface.
Term " can form the material of image " and refer to various goods of the present invention, and it includes but not limited to flexographic printing presoma, shelters element, photoresist, figuratum dielectric, figuratum three-dimensional structure, figuratum barrier film, figuratum mould (comprise for embossing and nano print application those), figuratum microfluidic device or structure and lithographic plate or presoma.This based article can any form, shape or size provide, and tool is with or without matrix, but generally at nanocrystal polyolefin and the radiation adsorber can in the layer of laser engraving with at least one thermoplastic elastomer (TPE).
Term " recipient element " refers to any material or matrix that can use flexographic printing component ink printing of the present invention.
Term " laser imaging " refers to laser engraving, and ' imaging ' refers to the ablation to background area, makes to remain untouched by curing ink with by the version region that flexographic printing prints.
Term " can laser engraving " relates to the composition or layer that can use suitable laser imaging, described laser produces heat and to cause in composition or layer localized variation fast in composition or layer, makes imaging region from physical separation the remainder of composition or layer and discharge and is collected rightly.Destruction is violence process, and it comprises and bursting out, and blast, tears, and decomposes, and volatilization is cracked, or produces the destructive processes of the material comprised in the wide region of one or more gases.This can distinguish with such as image transfer.Use " laser engraving " that also can be described as " ablation engraving " or " ablative engraving ", be embodied as the formation of picture or matrix.The non-imaging region of layer of laser engraving can not be removed on obvious degree or volatilize, and therefore forming the upper surface of matrix.
" elastomeric, form embossment can the layer of laser engraving " refers to the outmost surface of flexographic printing presoma, wherein forms matrix and is the first surface of the presoma being imaged radiation effects (struck).This layer of this paper is also referred to as the layer of laser engraving " can ".
Term " matrix " refer to provided by imaging and be designed to the design transfer of ink to all configural characteristics (topographical features) of the flexographic printing component of recipient element.Term " matrix bottom surface " refers to the bottom surface of matrix.Such as, can think that this bottom surface is that matrix is from the maximum dry degree of depth of upper space and can at 50 μm to 1000 μm and be generally in the scope of 100 μm to 800 μm.Matrix generally includes " valley ", and it is not by inking and have the degree of depth from upper space being less than the maximum sole degree of depth.
Except as otherwise noted, term " % by weight " refers to the composition of overall dry weight based on the composition residing for it or layer or the amount of material.
Term " adhesive " refers to can the summation of component of polymer of all thermoplasticity in the layer of laser engraving and thermoplastic elastomer (TPE), comprises thermoplastic elastomer (TPE) nanocrystal polyolefin.
Can the layer of laser engraving
The matrix using the present invention to obtain is formed at can in the layer of laser engraving, described can the layer of laser engraving comprise one or more thermoplastic elastomer (TPE) nanocrystal polyolefin as it main or leading component.Therefore, the layer of laser engraving can comprise the nanocrystal polyolefin of thermoplastic elastomer (TPE), based on total dried layer weight, its amount is at least 30 % by weight and at the most and comprise 100 % by weight, or typically at least 50 % by weight and at the most and comprise 98 % by weight.
In general, the dry thickness of layer of laser engraving at least 50 μm and at the most and comprise 4,000 μm can be generally at least 50 μm, or at least 200 μm and at the most and comprise 2,000 μm.
This layer of laser engraving can be substantially free of the polymer (such as styrene and the styrene group that is substituted) with side aryl.That is, not intentionally to the polymer that can add in the layer of laser engraving containing side styryl.This base polymer comprises polystyrene (comprising the homopolymers of styrene derivative), poly-(methyl styrene), the copolymer derived by the polymerization of vinyl benzene (styrene) and styrene derivative, aromatic vinyl or vinyl-arene at least partly and block copolymer or alkenyl aromatic polymer.Therefore, this base polymer in the layer of laser engraving, based on total dried layer weight, usually exist with the amount being less than 5 % by weight, and typically, this amount can be less than 1 % by weight.
In addition, this can the layer of laser engraving also containing chemical crosslinking as hereinbefore defined.Should be understood that by some methods, such as, by being exposed to radiation source (such as electron beam, γ radiation, or ultraviolet light) or by adding chemical cross-linking agent or reagent in said composition, realizing chemical crosslinking.In the present invention, should understand and this means to add chemical cross-linking agent in the layer of laser engraving not expressly to presoma.This type of chemical cross-linking agent is well known in the art, and comprises such as: peroxide, sulphur and sulfur-containing compound, light trigger, and other produces the compound of free radical.In addition, this type of chemical cross-linking agent can be acidic compound.Therefore, this can the layer of laser engraving or presoma usually not containing the chemicals that generation can be caused free radical or the acidic group be cross-linked.This type of chemical cross-linking agent, therefore based on total dried layer weight, usually exists with the amount being less than 0.5 % by weight, and is typically less than the amount of 0.1 % by weight.
Can the layer of laser engraving usually not be containing the reason of chemical crosslinking, this layer remains all thermoplasticities, and this makes it have good smelt flow so that it can be melted and again be formed as above-mentioned new flexographic printing presoma.
Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA is comprised as used, DMTA) or the known method of thermodynamic analysis (TMA) measure, for 10 DEG C usually can be less than or equal to and be typically less than or equal to 0 DEG C by the polyolefinic glass transition temperature of thermoplastic elastomer (TPE) nanocrystal in the layer of laser engraving.
The known method comprising differential scanning calorimetry (DSC) as used measures ground, for usually can having and be more than or equal to 40 DEG C and be preferably more than or equal the crystalline melt temperatures of 100 DEG C by the thermoplastic elastomer (TPE) nanocrystal polyolefin in the layer of laser engraving.
In another aspect, containing the polyolefinic formation elastomeric relief of thermoplastic elastomer (TPE) nanocrystal, can the layer of laser engraving have when logarithm draw time, higher than described can laser engraving layer fusion temperature temperature under, the G ' reduced continuously along with the reduction of frequency of oscillation and G " value.
Useful nanocrystal polyolefin includes but not limited to have 2 to 20 carbon atoms and typically is the homopolymers of the undersaturated alkene of ethylenic of 2 to 8 carbon atoms.This type of undersaturated alhpa olefin with at least 3 carbon atoms can have the alkyl side chain of various straight or branched, and any alkene can have other side chain, precondition is that this side chain can not adversely affect polyolefinic form or thermoplasticity and elastomer properties.Nanocrystal polymer also comprises the copolymer of the olefin repeat unit comprising at least two kinds of random sequences of difference.Such as, these copolymers can comprise derivative (polymerization) has at least 2 and the different alkene of 20 carbon atoms at the most random repeat unit from two or more, such as, the combination of the ethene of repetition in the polymer backbone in random order, propylene, butylene, octene and ENB repetitive.In this analog copolymer, a kind of olefin repeat unit can occupy the majority.Such as, propylene recurring units can account at least 50 % by mole of the polyolefinic total repetitive of nanocrystal and at the most and comprise 90 % by mole.Useful copolymer can have with alternately, the different repeat units of random or periodic sequence arrangement.In addition, these copolymers can be straight copolymers, block copolymer, tapered copolymer, block terpolymer, segmented copolymer, graft copolymer, branch copolymer comprise star-like, brush, combed and dendritic copolymers.
Other instantiation that can be used for the alhpa olefin preparing copolymer includes but not limited to: ethene, 1-propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-endecatylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbene, cetene, 1-heptadecene, 1-vaccenic acid, 1-19 carbene, 1-eicosylene (eicocene), 9-methyl isophthalic acid-decene, 11-methyl isophthalic acid-dodecylene, and 12-ethyl-tetradecene.
This copolymer also can comprise the total repetitive derived from unconjugated polyene of 20 % by mole at the most, described unconjugated polyene includes but not limited to: bicyclopentadiene, 1, 4-hexadiene, cyclo-octadiene, methene norbornene, ethylidene norbornene, vinyl norbornene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 4-ethyl-1, 4-hexadiene, 5-methyl isophthalic acid, 4-heptadiene, 5-ethyl-1, 4-heptadiene, 5-methyl isophthalic acid, 5-heptadiene, 6-methyl isophthalic acid, 5-heptadiene, 5-ethyl-1, 5-heptadiene, 4-methyl isophthalic acid, 4-octadiene, 5-methyl isophthalic acid, 4-octadiene, 4-ethyl-1, 4-octadiene, 5-ethyl-1, 4-octadiene, 5-methyl isophthalic acid, 5-octadiene, 6-methyl isophthalic acid, 5-octadiene, 5-ethyl-1, 5-octadiene, 6-ethyl-1, 5-octadiene, 6-methyl isophthalic acid, 6-octadiene, 7-methyl isophthalic acid, 6-octadiene, 6-ethyl-1, 6-octadiene, 4-methyl isophthalic acid, 4-nonadiene, 5-methyl isophthalic acid, 4-nonadiene, 4-ethyl-1, 4-nonadiene, 5-ethyl-1, 4-nonadiene, 5-methyl isophthalic acid, 5-nonadiene, 6-methyl isophthalic acid, 5-nonadiene, 5-ethyl-1, 5-nonadiene, 6-ethyl-1, 5-nonadiene, 6-methyl isophthalic acid, 6-nonadiene, 7-methyl isophthalic acid, 6-nonadiene, 6-ethyl-1, 6-nonadiene, 7-ethyl-1, 6-nonadiene, 7-methyl isophthalic acid, 7-nonadiene, 8-methyl isophthalic acid, 7-nonadiene, 7-ethyl-1, 7-nonadiene, 5-methyl isophthalic acid, 4-decadinene, 5-ethyl-1, 4-decadinene, 5-methyl isophthalic acid, 5-decadinene, 6-methyl isophthalic acid, 5-decadinene, 5-ethyl-1, 5-decadinene, 6-ethyl-1, 5-decadinene, 6-methyl isophthalic acid, 6-decadinene, 7-methyl isophthalic acid, 6-decadinene, 6-ethyl-1, 6-decadinene, 7-ethyl-1, 6-decadinene, 7-methyl isophthalic acid, 7-decadinene, 8-methyl isophthalic acid, 7-decadinene, 7-ethyl-1, 7-decadinene, 8-ethyl-1, 7-decadinene, 8-methyl isophthalic acid, 8-decadinene, 9-methyl isophthalic acid, 8-decadinene, 8-ethyl-1, 8-decadinene, 9-methyl isophthalic acid, 8-11 carbon diene etc.The example of useful nanocrystal homopolymers includes but not limited to: polyethylene, polypropylene, poly-(1-butylene), poly-(1-amylene), poly-(1-hexene), poly-(1-octene), poly-(1-decene), poly-(2-butylene), poly(4-methyl-1-pentene), poly-(vinyl cyclohexane), and other cyclic olefin polymer.
The example of useful nanocrystal copolymer includes but not limited to: the copolymer comprising at least propylene recurring units, comprise the copolymer of both propylene and ethylene repeating unit, comprise the copolymer of both ethene and butene repeat unit, comprise the copolymer of ethene, propylene and butene repeat unit, and comprise ethene and the copolymer both octene repetitive.The structure of repetitive can have any steric regularity, comprises atactic, isotaxy or syndiotaxy.
Equally usefully by co-polymerization by a small amount of, the such as functional group of polar group (such as >CO ,-OH and-COOH), introduce in nanocrystal polyolefin, to increase its adhesiveness to such as matrix, or to improve the compatibility of nanocrystal polyolefin and additive (such as plasticizer) and particulate (such as radiation adsorber, inorganic oxide and microcapsules).Other useful copolymer compositions can be have the alhpa olefin of 2-20 carbon atom and following copolymer: vinyl esters (such as vinylacetate or propionate), or there is Arrcostab or the unsaturated carboxylic acid such as acrylic acid of 20 carbon atoms at the most, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, or itaconic anhydride or acrylate or methacrylate such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl, isobutyl acrylate, n-butyl acrylate, 2-EHA, methyl methacrylate, EMA, isobutyl methacrylate, n-BMA, GMA, dimethyl maleate, or diethyl maleate, as long as the inclusion of these comonomers can not adversely affect the polyolefin form of material or elastomer properties and performance characteristics.
The commercial form of exemplary nano crystalline polyolefin can obtain from Mitsui Chemicals company (Tokyo) with Notio PN-2070 elastomer.This commercial product is the elastomer that propylene is dominated, and it has nanocrystalline structures, and described nanocrystalline structures is controlled by the characteristic of impact for the preparation of the metallocene catalyst of this polymer.This elastomer has the Component units of the propylene derived of 71 % by mole, and the residue repetitive of derived from ethylene and 1-butylene.This thermoplastic elastomers has following physical property: Shore A hardness (ASTM D2240) is 75, fusing point is 138 DEG C, density (ASTM D1505) is 867 kg/m3, glass transition temperature (Tg) is-29 DEG C, mist degree is 7%, be 7.0 g/10 min with smelt flow (MFR, ASTM D1238).Nanocrystal other useful commercial examples polyolefinic is the Notio product from Mitsui Chemicals America company (Rye Brook, NY.), and from the Engage product of Dow Chemical Ayer (MA).
Can use as being described in (but being not limited to) such as United States Patent (USP) 6,930,152 (people such as Hashimoto) and 7,253,234 (people such as Mori), with the known synthetic method in U.S. Patent Application Publication 2008-0220193 (Tohi), prepare the nanocrystal polyolefin that other is useful.
The layer of laser engraving can have the mixture of polymer, wherein one or more nanocrystal polyolefin, based on the dry weight of polymeric blends, with at least 30 % by weight and at the most and comprise 99 % by weight, and typically at least 50 % by weight and at the most and the amount comprising 97 % by weight exist.This type of mixture can comprise one or more non-nano crystalline polymers, and it comprises non-nano crystalline polyolefin.Therefore, in some embodiments, this layer of laser engraving can comprise the mixture of one or more thermoplastic elastomer (TPE) nanocrystal polyolefin and one or more non-nano crystalline polyolefins.This non-nano crystalline polymer also can be thermoplastic elastomer (TPE), semi-crystalline polymer, or it can be thermoplastic nonelastomeric's resin, and it exists can not adversely affect the amount using laser engraving, recuperability and physical property required for the present invention.Such as, this type of mixture can comprise thermoplastic elastomer (TPE) nanocrystal polypropylene (at least 50 % by weight and at the most and comprise 99 % by weight) and non-nano crystallization semi-crystalline polypropylene.Other non-nano crystalline polymer can be there is, as long as wittingly can in the layer of laser engraving by being included in containing cinnamic polymer.In some embodiments, the layer of laser engraving thermoplastic elastomer (TPE) nanocrystal polyolefin and the polyolefinic mixture of another kind of thermoplastic elastomer (TPE) nanocrystal can be comprised.In some embodiments, thermoplastic elastomer (TPE) nanocrystal polyolefin or non-nano crystalline polyolefin can have alternatively or all have branched structure.
Such as, this layer of laser engraving can comprise one or more thermoplastic polymers, such as, derived from the polyurethane resin of PIC and polyalcohol (such as polymer diol) or the reaction with polyamines.Other useful polymer comprises PIC, polybutadiene or polyisoprene elastomer, nitrile polymer, polychlorobutadiene, polyisobutene, and other butyl elastomers, any elastomer containing chlorosulfonated polyethylene, polysulfide, polyalkylene oxide, or polyphosphazene, the polymer of (methyl) acrylate, polyester, and other similar polymer known in the art.Although may desirably these non-nano crystalline polymers have elastomer properties, this be strictly required, as long as its existence can not adversely affect laser engraving required for the present invention, recuperability and physical property.In some embodiments, thermoplastic elastomer (TPE) nanocrystal polyolefin or described non-nano crystalline polymer can have branched structure.
The polyolefinic mixture of dissimilar nanocrystal can be useful in the layer of laser engraving.Importantly consider miscibility and the compatibility of component polymer when preparing mixture, because these are by the physical property of the final material of impact and performance.
Export for use peak energy and be near infrared laser diode and carry out infrared imaging, described material must containing in dyestuff or the specific radiation absorber material of pigment form, the absorbing laser energy of described dyestuff or pigment and exposure photon is converted to heat energy.Because most of polymeric material at least 750 nm and at the most and the wavelength comprising 1400 nm direct radiation-absorbing, so preparation is also can comprise at least one infrared (IR) absorbent with the flexographic printing presoma of laser emission engraving at these wavelengths.This type of infrared absorbing agents can be dyestuff or the pigment (such as carbon black) with specific absorption peak, and it is panchromatic for being wherein absorbed on whole near infrared spectrum.
This layer of laser engraving can comprise radiation adsorber further, and based on total dried layer weighing scale, its amount is at least 0.5 % by weight and at the most and comprise 35 % by weight, and particularly at least 3 % by weight and at the most and comprise 15 % by weight.
Useful especially absorber of infrared radiation can respond the exposure from infrared laser.If needed, the mixture of the absorber of infrared radiation of identical or different type as described below can be used.Wide region absorber of infrared radiation can be used for the present invention, comprise carbon black and other absorbs infrared organic or inorganic pigment (the sour cyanines in the side of comprising (squarylium), cyanine, merocyanine, indolizine, pyrans, metal phthalocyanine and metal dithionite heterocyclic pentene (metal dithiolene) pigment) and iron and other metal oxide.Other useful absorber of infrared radiation comprises conductive carbon black and the carbon black by solubilising well known in the art or compatibilizing groups functionalisation of surfaces.Connect skill to carbon black such as FX-GE-003 (Nippon Shokubai manufactures) that is hydrophilic, non-ionic polymers, or be also useful by the carbon black such as CAB-O-JET 200 or CAB-O-JET 300 (Cabot Corporation manufactures) of anionic group functionalisation of surfaces.The example of useful carbon black comprises: Mogul L, Mogul E, Emperor 2000, Vulcan XC-72, Sterling C, Black Pearls 700 and 1300, Monarch 800 and 1400 and Regal 330 and 400, all from Cabot Corporation (Boston MA).Other useful pigment includes but not limited to: phthalein viridescent (Heliogen Green), nigrosine (Nigrosine Base), iron oxide (III), transparent ferric oxide, magnetic paint, manganese oxide, Prussian blue and Paris blue.Other useful absorber of infrared radiation is CNT, such as list and multi-walled carbon nano-tubes, graphite, Graphene (graphene), and porous graphite.The atomic thickness that Graphene is made up of the carbon atom being arranged in honeycomb, two-dimensional sheet.It can be regarded as the construction unit of other graphitic carbon allotropes all of different dimensions, and such as, graphite is made up of the graphene sheet overlie one another.The example of useful Graphene includes but not limited to: from the xGnP graphene nano platelet of XG Sciences (MI), comprises average thickness for about 6-8nm and typical earth surface area is 120 to 150 m 2the M grade particles of/g, and from the Vor-X functionalized graphite alkene Nano sheet material of Vorbec Materials (MD), and from the Graphene of Graphene Industries (UK) and Graphene Laboratories (MA).
Other useful absorber of infrared radiation (such as λ max is the organic dyestuff of at least 800 nm) is described in: United States Patent (USP) 4, 912, 083 (people such as Chapman), 4, 942, 141 (people such as DeBoer), 4, 948, 776 (people such as Evans), 4, 948, 777 (people such as Evans), 4, 948, 778 (DeBoer), 4, 950, 639 (people such as DeBoer), 4, 950, 640 (people such as Evans), 4, 952, 552 (people such as Chapman), 4, 973, 572 (DeBoer), 5, 036, 040 (people such as Chapman) and 5, 166, 024 (people such as Bugner).
When using pigment or particulate infrared absorbing agents, should be realized that, the comparatively fine dispersions of minimum particle will provide best ablation characteristics resolution ratio and ablation sensitiveness.Specially suitable is have diameter to be less than those of 1 μm.Dispersant and surperficial official ligand can may be used for the quality improving carbon black or metal oxide or pigment dispersion, make it possible to achieve throughout can laser ablation, evenly the mixing of the layer intermediate infrared radiation absorption compound that forms embossment.
Of the present inventionly the flexographic printing presoma of laser engraving or other material that can form image can comprise one or more thermoplastic elastomer (TPE) nanocrystal polyolefin and radiation adsorber (such as absorber of infrared radiation) in the layer of laser engraving identical.In this type of embodiment, one or more nanocrystals are polyolefinic exists total amount at least 30 % by weight and at the most and comprise 98 % by weight.Radiation adsorber, can at least 2 % by weight and at the most and comprise 35 % by weight based on total dried layer weight, and typically at least 3 % by weight and at the most and the amount comprising 20 % by weight exist.
This layer of laser engraving can comprise chemical non-activity particle or microcapsules further, and based on total dried layer weighing scale, its amount is at least 2 % by weight and at the most and comprise 50 % by weight, or typically at least 5 % by weight and at the most and comprise 25 % by weight.Term " non-activity " means this particle or microcapsules are chemically inert, and not with polymeric binder or radiation adsorber chemical reaction.In addition, the particle of these non-activities or microcapsules are not containing radiation adsorber and not absorbing laser radiation.But its existence can the engineering properties of reinforcement material, and the hardness of reinforcing material, or the cohesive reducing material and ablation debris, make it possible to the cleanliness factor being easier to garbage collection and improving laser engraving component.
The inorganic particle of non-activity comprises various inorganic filler material, it includes but not limited to: silica, titanium dioxide, and aluminium oxide, and particle (such as finely particulate silica, fumed silica, celelular silica, barium sulfate, calcium carbonate, calcium sulfate, zinc oxide, mica, talcum (magnesium silicate hydrate), surface-treated silica (Cab-O-Sil that Aerosil and the Cabot Corporation that Degussa sells sells), zeolite, with silicate ore and clay (such as bentonite, montmorillonite, and kaolinite), alumina silicate, halloysite and halloysite nanotube, with superfine powder (the amorphous silicic acid magnesium cosmetics microsphere that such as Cabot and 3M Corporation sells).
In some embodiments, the microcapsules of non-activity can be dispersed in can in the layer of laser engraving, such as, in thermoplastic elastomer (TPE) nanocrystal polyolefin.The microcapsules of non-activity also can be described as " hollow globule ", " microsphere ", " microvesicle " or " microballoon ".Specific examples of such components can comprise double glazing globule or have the globule of core of thermoplastic polymer shell and air or volatile liquid such as isopentane and iso-butane.Such as, the microcapsules of non-activity can as United States Patent (USP) 4,060,032 (Evans) and 6,989, those description in 220 (Kanga) design, or as such as United States Patent (USP) 6,090,529 (Gelbart) and 6, be designed to plastic microsphere with describing in 159,659 (Gelbart).
The microsphere of non-activity can be hollow, or is filled by the solvent of non-activity, and is conducive to can engraving in the layer of laser engraving, because they decrease the energy needed for engraving.The microsphere of non-activity is formed by following usually: inorganic glass materials (such as silica glass, magnesium silicate glass); Or the thermoplasticity polymeric shell material of non-activity (such as styrene or acrylic copolymer or vinylidene chloride copolymer).
Non-activity, non-porous polymeric composition granule also can the above-mentioned amount for other particles of types mix can in the layer of laser engraving.
Optional supplementing also can include but not limited to plasticizer in the layer of laser engraving, colouring agent (such as dyestuff and pigment), antioxidant, antiozonant, stabilisation compound, dispersing aid, surfactant, and adhesion promoter, as long as they do not disturb the efficiency of laser engraving, or these inclusion can not adversely affect the polyolefin form of material or elastomer properties or its recovery ability.The example of plasticizer can comprise low-molecular-weight polyolefin, polyester or polyacrylate, fluorinated compound, silicone compounds, noncrosslinking liquid rubber and oils, liquid ethylene-propylene, liquid polybutene, liquid polypropylene, or these mixture.
Can the flexographic printing presoma of laser engraving
This can the layer of laser engraving can by comprising one or more elastomer resins, optionally the formula of one or more coating solvents is formed, to provide elastic composition, described elastomer resin comprises at least one thermoplastic elastomer (TPE) nanocrystal polyolefin, and optionally radiation adsorber and other additive.This formula can be formed as the layer of self-supporting or be arranged on (as described below) in suitable matrix.This layer can be formed in any suitable manner, such as by methods known in the art to coating in this matrix, flow coat, spraying or topple over a series of formula and drying to form layer, smooth or bending sheet material or seamless printing sleeve.Alternatively, this formula can be pressed shaping, injection moulding, melt extrudes, coextrusion or melting are rolled into suitable layer or ring (sleeve) and optionally to be adhered to or be laminated in matrix and cooling to form layer, sheet material that is flat or that bend or seamless printing sleeve.The flexographic printing presoma of sheet-form can be wrapped in and prints on post and optionally melt to form seamless printing presoma in edge.
Can the flexographic printing presoma of laser engraving can comprise the self-supporting comprising nanocrystal polyolefin and other additive can the layer (as defined above) of laser engraving.Suchly can the layer of laser engraving not need independent matrix to have physical integrity and intensity.In such an implementation, can the layer of laser engraving enough thick, and controlling laser engraving in such a way, to make the matrix degree of depth be less than integral thickness, such as, is at the most 80% of this layer of integral thickness.
Total dry thickness of flexographic printing plates presoma of the present invention is at least 500 μm and at the most and comprise 6,000 μm or typically at least 1,000 μm and at the most and comprise 3,000 μm.As implied above, all this thickness can by can the layer of laser engraving form, but when there is matrix or other layer, can the layer dry thickness of laser engraving typically be total dry presoma thickness at least 10% and at the most and comprise 95%.Flexographic printing elements presoma usually can have at least 2 mm and at the most and comprise 20 mm can the layer of laser engraving.Flexographic printing cylinder also by have suitable can the layer thickness of laser engraving.
Can by can the layer of layer (as mentioned above) of laser engraving be arranged on another with produce thicker can the layer of laser engraving.These layers can be identical, or can be different on composition, and wherein they are relative to the polyolefinic amount of nanocrystal, comprise the additive (such as particulate, microcapsules, radiation adsorber, polymer) of different amount and type.Different nanocrystal polyolefin or its combination also may be used in different layers.Such as, the layer containing hollow microspheres or microvesicle can be arranged on can the below of laser engraving layer containing going up most of hollow microspheres.
But, in other embodiments, this can the flexographic printing presoma of laser engraving comprise that there is into the suitable dimensionally stable of image side and non-imaged side, non-can the matrix of laser engraving.This matrix has at least one being arranged on in the matrix of image side can the layer (as mentioned above) of laser engraving.In most of embodiment, can the layer of laser engraving be set directly in matrix.Suitable matrix includes but not limited to: the polymeric membrane of dimensionally stable, aluminium flake or aluminum barrel, form of glass fibers, transparent form, pottery, weaves and non-woven fabric, or the laminate of polymeric membrane (from condensation or addition polymer) and metal sheet, the laminate of such as polyester and aluminium flake or the laminate of polyester/polyamide, the laminate of the supporter of polyester film and plastic or viscosity, or polyester and weave the laminate with non-woven fabric.Polyester, Merlon, polyvinyl or polystyrene film can be used.Useful polyester includes but not limited to gather (PETP) and poly-(polyethylene naphthalate).This matrix can have any suitable thickness, but especially for polymeric matrices, and they are generally at least 0.01 mm or at least 0.05 mm and at the most and comprise 0.3 mm thick (dry thickness).With adhesion layer, elastic composition can be fixed in matrix.Such as, the thin conductive layer of poly-(3,4-ethene-dioxythiophene) (PEDOT), polyacetylene, polyaniline, polypyrrole or polythiophene, indium tin oxide (ITO) and Graphene or film can be arranged on matrix and can between the layer of laser engraving.
The non-imaged side of the matrix that can be made up of flexible rubber or foam or other plastic layer may have non-can the back coating of laser engraving.This back coating can exist between matrix and printing pressing roll, provide adhesion and provide extra plasticity to the print-member of gained, or reduces or control the curling of print-member.In addition, this back coating can catoptric imaging radiation or transparent to it.If needed, by the laser of the identical type with this one-tenth image side of engraving or by with dissimilar laser, this back coating also can laser engraving.This back laser engraving may be used for recording such as customizing messages or metadata.
Therefore, describedly the flexographic printing presoma of laser engraving can contain one or more layer, but presoma is simpler, it more easily reclaims the flexographic printing component of gained.Except can except the layer of laser engraving, matrix and can be able to existing between the layer of laser engraving of going up most is non-can the elastomer rubber layer (such as, cushion) of laser engraving.In some embodiments, can exist and extra smoothness or the better covering that receives of ink or smooth layer are provided, its be arranged on comprise that thermoplastic elastomer (TPE) nanocrystal is polyolefinic can on the layer of laser engraving.When there is this type of extra play (and matrix) and when needing to reclaim this flexographic printing component, usually they being peeled off from containing the polyolefinic laser engraving layer of nanocrystal, make laser engraving layer can be easy to melting and recovery.，
Can prepare in every way by the flexographic printing presoma of the laser engraving material that maybe can form image, such as, coating or spray this in a suitable solvent can the layer formula of laser engraving dry to matrix.Alternatively, this layer of laser engraving can be able to be that pressing is shaping, injection moulding, melt extrude, extrude rear calendering or be coextruded into suitable layer or ring (sleeve) and adhere to or be laminated to matrix to form continuous print layer, smooth or bending sheet material or seamless printing sleeve.The layer of sheet-form can be wrapped on printing cylinder and optionally in edge's fusing to form jointless flexographic printing sleeve.
Can means known in the art be passed through, use available machinery such as to use belt grinding machine, the cartridge type grinding machine of abrasive wheel or paper, to the flexographic printing presoma of laser engraving carrying out mechanical lapping.Grinding can laser engraving surface or non-ly can to carry out on the surface by laser engraving, to guarantee that thickness is homogeneous, or it can be able to carry out realizing required surface roughness by laser engraving on the surface, and this will improve ink and soak and shift.
The flexographic printing presoma of laser engraving also can be configured in backplate, have suitable protective layer or synovial membrane (having release property or interleaving agent), described backplate was removed before laser engraving.This type of protective layer can be that polyester film [such as poly-(PETP)], polyethylene or similar film are to form backplate.
Laser engraving and printing
Therefore, the present invention can carry out the suitable flexographic printing presoma of laser engraving by using laser engraving radiation, in flexographic printing component, provide matrix.This type of presoma may be used for forming flexographic printing plates, flexographic printing elements or flexographic printing cylinder.
Use one or more suitable laser diode (such as infra-red laser diode), the imaging of flexographic printing presoma can be realized to provide required matrix.Gained flexographic printing component can have the matrix having geometric properties or several relief features, or it can have shape or the irregular matrix of outward appearance.
Usually suitable imaging Laser or laser array can be used to apply to carve energy, described laser or laser array such as but not limited to: gas laser is as CO 2laser, near-infrared laser be near-infrared radiation radiation diode, diode laser matrix, Nd-YAG laser, fiber semiconductor laser, fiber coupling semiconductor laser diode or other laser array such as.There is provided the engraving of the matrix of the degree of depth at least 100 μm to be desirable, depth capacity is the matrix of 300 μm to 1000 μm is more desirable.The degree of depth between the characteristics of image that should be understood that tight spacing will be less than this depth capacity.When matrix or non-can carving layer be present in can below the layer of laser engraving time, matrix can have can laser engraving layer original depth at the most 100% depth capacity.In this case, if can the layer of laser engraving be completely removed in imaging region, then the bottom surface (floor) of matrix can be matrix.If the matrix of use, then matrix can have can laser engraving layer original depth at the most 80% depth capacity.
The laser instrument operated under being generally used in the wavelength of at least 700 nm, and useful especially be at least 800 nm and at the most and the laser instrument operated under comprising the wavelength of 1250 nm.This laser should have sufficiently high intensity, and the pulse that caused by relative motion between laser and presoma or effective impulse are roughly adiabatically deposited at impulse duration.Usually, be used in presoma upper space place and at least 1 J/cm is provided 2at least one laser of minimum flux level realize laser engraving, and typically at least 20 J/cm 2at the most and comprise 1000 J/cm 2or at least 50 J/cm 2at the most and comprise 1500 J/cm 2energy under carry out infrared laser engraving.
Such as, diode laser, the array of diode laser be connected with optical fiber, Nd-YAG laser instrument, fibre laser, carbon dioxide gas laser or semiconductor laser can be used to carry out laser engraving.This quasi-instrument and the condition that they use are well known in the art and can derive from many commercial source easily.Detailed description can see U.S. Patent Application Publication 2010/0068470A1 (Sugasaki), 2008/018943A1 (people such as Eyal) and 2011/0014573A1 (people such as Matzner), and all patents are incorporated at this by quoting.
Therefore, can comprise with the system forming flexographic printing component for laser engraving flexographic printing plates presoma:
Can the flexographic printing presoma of laser engraving for what provide matrix as herein described, and
One or more laser engraving radiation source, it is directed to provide this can the laser engraving of layer of laser engraving.Especially, this layer of laser engraving can comprise absorber of infrared radiation and this one or more laser engraving radiation source provides infra-red radiation.
This system can comprise platform further, install thereon be used for laser engraving can the flexographic printing presoma of laser engraving.In addition, within the system, one or more laser engraving radiation source can be selected from laser diode, multiple emitter laser diode, laser bar, laser instrument heap (laser stack), fibre laser, and its combination.
The laser engraving to matrix can be carried out in all cases.Such as sheet-like flexible version printing presoma can be imaged, and uses on demand, or is wrapped in before imaging on printing post or drum forms.Flexographic printing presoma also can be the printing sleeve that can directly be installed in laser image forming apparatus.
During imaging, major part engraving remove product be particulate and gas or volatile ingredient combination and easily through vacuum collecting so as to dispose or chemical treatment.Any residual solid fragment on engraving component can use vacuum or washing to collect similarly.
After imaging, if elastomeric upper space still stickness, then can use methods known in the art, make the flexographic printing component of gained stand optional to go glutinous step.
During printing, use known method by the flexographic printing component inking of gained, and use flexographic presses, this ink is transferred to suitable recipient element rightly, such as paper, plastics, fabric, cardboard or cardboard.
If needed after printing, then can clean the galley of imaging or printing sleeve and make the melt surface of engraving and recovery (vide infra).Such as, if observe defect in matrix, then the polyolefinic laser engraving layer melting of thermoplastic elastomer (TPE) nanocrystal and the recovery of any laser engraving flexographic printing component can be comprised before printing.
Recovery method
Before printing or afterwards, can clean and re-use this flexographic printing component, and printing cylinder can be scraped off or clean and can the layer (before imaging) of laser engraving or the layer (after imaging) of laser engraving re-use by reclaiming.Such as, if there is undesirable defect in this layer, then can the layer of laser engraving carved before, by its melting and recovery.Alternatively, if engraving process produce mistake or need to revise image, then can engraving after but printing before reclaimed.Finally, the layer of engraving can be recovered after impression terminates.Alternatively, can by flexographic printing elements molding and casting mold more again by this thermoplastic elastomer (TPE) nanocrystal polyolefin layer of melting, to allow imaging and non-imaged areas merge and generate fresh homogeneous surface, this surface will become flexographic printing presoma when cooling.Optionally, this unsalted surface can grind with as above describing.Unsalted surface can be exposed to subsequently in laser ablation and to print new images.
Following exemplary process may be used for reclaiming or re-using laser engraving component of the present invention:
1. clean to remove any residual ink or fragment from physical separation thermoplastic elastomer (TPE) as herein described nanocrystal polyolefin layer composition other layer any of matrix and existence;
2. thermoplastic elastomer (TPE) nanocrystal polyolefin layer composition is cut the form being easy to process chopping, cut or grind to form such as fritter or powder;
3. this fritter or powder are arranged on suitable treatment temperature to be formed in the fused mass batch mixer of fused mass or extruder or other suitable device to delivering to; With
4. new flexographic printing plates presoma is extruded, rolls or be molded as to this fused mass.
Optional exemplary process may be used for the flexographic printing component reclaiming or re-use laser engraving of the present invention below.
1. clean to remove any residual ink or fragment from physical separation thermoplastic elastomer (TPE) as herein described nanocrystal polyolefin layer composition other layer any of matrix and existence;
2. by thermoplastic elastomer (TPE) nanocrystal polyolefin layer composition dissolves in suitable solvent or solvent mixture to form solution;
3. this solution is coated with, sprays or be poured in suitable matrix to form layer or multilayer; With
4. one or more layers of this coating dry are to provide new flexographic printing plates presoma.
Still another exemplary process that may be used for the flexographic printing elements reclaiming or re-use laser engraving of the present invention comprises:
1. the sleeve used be installed on suitable runing rest and clean this surface to remove any residual ink or fragment;
2., such as when this device rotates to guarantee even, scrape off or shave off the skin of the aequum of thermoplastic elastomer (TPE) nanocrystal polyolefin layer;
3. collect the material removed and it is arranged on suitable treatment temperature to be formed in the fused mass batch mixer of fused mass or extruder or other suitable device to delivering to;
4. this fused mass is expressed in new flexographic printing presoma, or used, on the flexographic printing elements scraped; With
5. optionally grind this new surface to provide surface roughness needed for flexographic plate sleeve presoma and homogeneous thickness.
Still other method for reclaiming or re-use the flexographic printing elements of laser engraving of the present invention comprises:
1. the sleeve used be installed on suitable runing rest and clean this surface to remove any residual ink or fragment;
2. the feature that the skin heating the thermoplastic elastomer (TPE) nanocrystal polyolefin layer of this sleeve is carved with melting;
3. use the outer surface of hot this flexographic printing elements of casting mold again to form smooth homogeneous surface; With
4. optionally grind this new surface to provide surface roughness needed for flexographic printing elements presoma and homogeneous thickness.
The equipment that may be used for the step realizing recovery method described above includes but not limited to: single screw extrusion machine, double screw extruder, be equipped with the extruder of template, this batch mixer of Bradley (Brabender compounders), injection model forming machine, calender device, list or twin screw helical bore, batch mixing extrusion device, prilling granulator, sheet material extrusion device, cuts and chops and regrinding device.Miscellaneous equipment comprises solution coater and drying device.
Flexographic printing presoma of the present invention can be designed for this type of flexographic printing plates presoma of laser engraving to form a part for the system of flexographic printing component.Except presoma, this system can comprise at least one or more laser engraving radiation source, and it is directed to provide can the laser engraving of layer of laser engraving.Described by useful laser engraving source has above, other source is apparent for a person skilled in the art.A kind of useful system is described in U.S. Patent Application Publication 2011/0014573 (above).This laser engraving system comprises one or more laser engraving radiation source, and particularly precursor have two can the layer of laser engraving time, comprise two laser engraving radiation sources.
This system can comprise platform further, and installing thereon can laser engraving flexographic printing presoma, for laser engraving.This type of platform can comprise such as coiled material (move or do not move), cylinder or rotary drum.Described laser engraving radiation source (such as the source of infrared radiation) can provide with one or more laser instrument, such as it is from the hybrid optical imaging head with at least two group radiation sources, as such as described in U.S. Patent Application Publication 2008/0153038 people such as () Siman-Tov, described one or more laser instrument uses suitable control device to control.
Described one or more laser engraving radiation source can be selected from laser diode, multiple emitter laser diode, laser bar, laser instrument pile, fibre laser, and combination.In a particular embodiment, this presoma the layer of laser engraving can comprise absorber of infrared radiation and this one or more laser engraving radiation source provides infra-red radiation.
Such as United States Patent (USP) 6 is described in for providing other system of matrix by laser engraving, 150,629 (Sievers) and 6, in 857,365 people such as () Juffmger and U.S. Patent Application Publication 2006/0132592 (Sievers), 2006/0065147 (Ogawa), 2006/0203861 (Ogawa) and 2008/0153038 (above), 2008/018943A1 (above) and 2011/0014573A1 (shown above).
The invention provides at least following embodiment and combination thereof, but will understand from instruction of the present disclosure as technical staff, consider that other combination of feature is within scope of the present invention:
1. can the flexographic printing presoma of laser engraving for what provide matrix, described presoma comprise at least one elastomeric, formed embossment, can the layer of laser engraving, described layer comprises thermoplastic elastomer (TPE) nanocrystal polyolefin.
2. embodiment 1 can the flexographic printing presoma of laser engraving, wherein said elastomeric formation embossment, can the layer of laser engraving there is G ' and G " modulus (moduli); when logarithm draw time; higher than this can laser engraving layer fusion temperature temperature under, this G ' and G " modulus reduces continuously along with the reduction of frequency of oscillation.
3. embodiment 1 or 2 can the flexographic printing presoma of laser engraving, wherein said can the layer of laser engraving with at least 30 % by weight and at the most and the amount comprising 100 % by weight comprises described thermoplastic elastomer (TPE) nanocrystal polyolefin.
4. any one of embodiment 1 to 3 can the flexographic printing presoma of laser engraving, wherein saidly the layer of laser engraving can comprise the mixture of polymeric material, the mixture of described polymeric material comprise at least 30 % by weight and at the most and comprise 99 % by weight thermoplastic elastomer (TPE) nanocrystal polyolefin.
5. any one of embodiment 1 to 4 can the flexographic printing presoma of laser engraving, wherein saidly the layer of laser engraving can comprise the mixture of one or more thermoplastic elastomer (TPE) nanocrystal polyolefin and one or more non-nano crystalline polyolefins.
6. any one of embodiment 1 to 5 can the flexographic printing presoma of laser engraving, wherein saidly the layer of laser engraving can comprise the chemical cross-linking agent being less than 0.1 % by weight.
7. any one of embodiment 1 to 6 can the flexographic printing presoma of laser engraving, wherein can the layer of laser engraving be substantially free of containing styrene or the polymer of styrene group that is substituted.
8. any one of embodiment 1 to 7 can the flexographic printing presoma of laser engraving, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin has the glass transition temperature being less than or equal to 10 DEG C.
9. any one of embodiment 1 to 8 can the flexographic printing presoma of laser engraving, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin is the copolymer of the olefin repeat unit comprising at least two kinds of different random sequences.
10. any one of embodiment 1 to 9 can the flexographic printing presoma of laser engraving, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin is selected from substantially by the group of the following polymer formed: the polyolefin comprising at least propylene recurring units, comprise the polyolefin of ethylene repeating unit and octene repetitive, comprise the polyolefin of ethylene repeating unit and propylene recurring units, and comprise the polyolefin of ethylene repeating unit, propylene recurring units and butene repeat unit.
Any one of 11. embodiments 1 to 10 can the flexographic printing presoma of laser engraving, wherein saidly the layer of laser engraving can go back the radiation adsorber that packet content is at least 0.5 % by weight.
Any one of 12. embodiments 1 to 11 can the flexographic printing presoma of laser engraving, wherein saidly can the layer of laser engraving also to comprise as the carbon black of radiation adsorber, inorganic or organic pigment, CNT, Graphene, λ maxfor organic dyestuff or these any combination of at least 800 nm.
Any one of 13. embodiments 1 to 12 can the flexographic printing presoma of laser engraving, wherein saidly the layer of laser engraving can go back chemical non-activity particle or the microcapsules that packet content is at least 2 % by weight.
Any one of 14. embodiments 1 to 13 can the flexographic printing presoma of laser engraving, its also comprise arrange thereon elastomeric, form embossment can the matrix of layer of laser engraving.
15. materials that can form image, it comprises thermoplastic elastomer (TPE) nanocrystal polyolefin and radiation adsorber.
The material of the formed image of 16. embodiments 15, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin and radiation adsorber be in identical can in the layer of laser engraving, and described nanocrystal polyolefin with at least 30 % by weight and at the most and the amount comprising 98 % by weight be present in described can in the layer of laser engraving.
The material of the formed image of 17. embodiments 15 or 16, wherein said radiation adsorber is infrared radiation absorption body.
18. methods that matrix is provided in flexographic printing component by laser engraving, it comprise by any one of embodiment 1 to 14 can the flexographic printing presoma Imagewise exposure of laser engraving in laser engraving radiation, to provide the component of the flexographic printing with matrix.
The method of 19. embodiments 18, it provides the flexographic printing component with matrix, and described matrix has at least 50 and at the most and comprise the maximum dry degree of depth of 1000 μm.
The 20. flexographic printing components with the matrix provided by laser engraving, described flexographic printing component comprises matrix in comprising in the polyolefinic laser engraving layer of thermoplastic elastomer (TPE) nanocrystal of definition any one of embodiment 1 to 14.
The flexographic printing component of 21. embodiments 20, wherein said laser engraving layer is positioned in matrix.
The method of 22. flexographic printings, it comprises:
By described in any one of embodiment 1 to 14 and 18 to 21 can the flexographic printing presoma Imagewise exposure of laser engraving in laser engraving radiation, to provide the component of the flexographic printing with matrix, and
Use the described flexographic printing component being used for flexographic printing.
23. for laser engraving flexographic printing plates presoma to form the system of flexographic printing component, described system comprises:
Can the flexographic printing presoma of laser engraving for what provide matrix any one of embodiment 1 to 14, and
One or more laser engraving radiation source, its be directed to provide described can the laser engraving of layer of laser engraving.
The system of 24. embodiments 23, it also comprises platform, installs on the platform described the flexographic printing presoma of laser engraving to be used for laser engraving.
The system of 25. embodiments 23 or 24, wherein said one or more laser engraving radiation source is selected from laser diode, multiple emitter laser diode, laser bar, and laser instrument is piled, fibre laser, and combination.
System any one of 26. embodiments 23 to 25, wherein saidly the layer of laser engraving can comprise absorber of infrared radiation and described one or more laser engraving radiation source provides infra-red radiation.
Specific embodiments
There is provided following examples to illustrate practice of the present invention, be not intended to limit the present invention by any way.
Inventive embodiments 1:
By thermoplastic elastomer (TPE) (TPE) nanocrystal polyolefin grain (36g, Notio PN-2060, from Mitsui Chemicals America company, Rye Brook, NY) with carbon black powders (2.3g, Mogul L, from Cabot Corp Boston, MA) combine, and at this blender of Bradley (ATR-2120, be configured with 3 thermals treatment zone and high shear drum-type blade) 200 DEG C of melting mixing 7 minutes, remove from this blender, allow it cool.This produces the Notio PN-2060 of 94 % by weight and the carbon black of 6 % by weight.The sample (3.5g) of this mixture is incorporated into side there is 300FN Kapton sheet material so that release aluminum dipping form in, and use Carver press (model #_3393) group to be pressed into writing board shape through 5 minutes at 3000psi (20 MPa) 220 DEG C.The assembly of mould and its content is being set as colding pressing 30 minutes in another Carver press that the pressure of 20 MPas does not heat subsequently.Gained can the flexographic printing plates presoma size of laser engraving to be that 75 × 75mm is about 0.8mm thick.
Laser engraving:
Use 5.3 watts of spot size 80 μm, the single mode ytterbium fibre laser of 1064nm pulsation, imaging this can the flexographic printing plates presoma of laser engraving.Pulsewidth is for about 30nsec and pulse recurrence rate is 20kHz.This imaging contains the spot (patch) of 1cm × 1cm, and described spot uses laser beam speed grid process (rastered) under 800dpi of 13 to 6.5 inch per seconds (33.02 to 16.5cm/sec), produces 51J/cm 2to 102J/cm 2corresponding flux.The ratchet backstop micrometer of self non-rotating shaft (ratchet stop micrometer) is used to measure the degree of depth of ablation spot.As shown in Table I, when laser flux is 102J/cm 2time engraving the carved image degree of depth be 240 μm.
Swelling test:
Another test in, weigh diameter be 1.2 cm can laser engraving flexographic printing plates precursor samples block and be submerged in the mixture of isopropyl alcohol (80 % by weight) and ethyl acetate (20 % by weight).Precursor samples is placed 24 hours, remove, and blot (blotted dry), weigh again subsequently.Percent swell is determined by following equation, and outcome record is in lower Table I.
Swelling %=100 × { [example weight after submergence]-[initial weight of sample] }/[initial weight of sample]
The second flexographic printing plates presoma is prepared in the same manner as above-mentioned, except gained size is 12cm × 20cm, thick 0.8mm.This precursor samples is laminated to side to have on the thick PET of the 0.265mm of adhesion layer [poly-(PETP)] support member.Gained assembly is installed on rotary drum, and uses the engraving system with the multiple Fiber-coupled laser diode (respectively about 10 watts) launched at about 915nm place to carry out laser engraving under the resolution ratio of 150lpi (OK/inch).Use flexographic presses (Comco Cadet 700) and from the solvent-based cyan ink of Sun Chemical Corporation by the imaging flexographic lithographic printing plate (component) of gained for being printed onto polyethylene film.
Inventive embodiments 2-8:
Use melting is molded, preparation has can the flexographic printing plates presoma of the present invention of layer of laser engraving, use 5.3 watts, the single mode ytterbium fibre laser of 1064nm pulse carries out laser engraving to it, and as inventive embodiments 1 describes in the same manner, it is made to stand swelling test, except the gained weight rate of TPE nanocrystal polyolefin and carbon black is 93:7, (Notio product is from Mitsui Chemicals America company (Rye Brook with the polyolefinic name of product of nanocrystal, NY), Engage product is from Dow Chemical) be different, shown in following Table I.Laser flux is 102J/cm 2time engraving the depth value of matrix also record in tablei.
The rheology test of inventive embodiments 2:
With describe in inventive embodiments 2 identical, prepare the polyolefinic flexographic printing plates precursor samples of thermoplastic elastomer (TPE) nanocrystal.Use cutter edge drill (knife edged bore), stamp out the diameter disk of 25mm from precursor samples.Sample disk is packed into (from TA Instruments, DE, USA) in Rheometrics RMS-800 mechanical spectrometer.Use the small amplitude oscillation of the piling plate geometries (pallet plate geometry) of 25 mm to move, measure viscosity and the elastic response of precursor samples.For crosslinked material, the piling plate geometries (having the serration plate of the dark cut portion of 0.25 mm) of modification is used to prevent precursor samples slip onboard.Measure little calibration factor to associate so that serration plate response is responded with parallel-plate.In all cases, at room temperature sample disk is seated between presoma, is heated to 200 DEG C, and make it balance.Between the temperature rising stage, monitoring thermal expansion is to guarantee that normal force remains on 1000 below g.Under the measuring tempeature of 200 DEG C, be separated normal force to maintain by adjustment presoma and be less than 100 g, use low applying strain to guarantee that this response is in Linear Viscoelastic Region (linear viscoelastic regime), and moment of torsion is enough high to provide enough signal strength signal intensities.Some different strain amplitudes are used to measure best setting.During Rheological Characterization, use waiting in logarithm step (equal logarithmic step) of strain controlling the oscillating probe frequency put in precursor samples to be changed from 100 radian per second to 0.1 radian per seconds, and measure modulus (G ' and G ") at each frequency.Fig. 1 draws while logarithm is shown G ' and the G of precursor samples " frequency response of modulus.This image fully characterizes the viscoelastic response of material.Alternatively, can in equivalently represented method display data: complex viscosity and damping factor (also referred to as loss tangent).
Comparative example 1:
Prepare flexographic printing plates presoma, molded, and use 5.3 watts, the single mode ytterbium fibre laser laser engraving of 1064nm pulse, and as description in inventive embodiments 1, it is made to stand swelling test, except the gained weight rate of adhesive and carbon black is 93: 7, and adhesive is non-nano crystallization, semi-crystalline polypropylene (isotaxy, Mn=250,000, product #_182389, from Sigma-Aldrich St. Louis, MO).Laser flux is 102J/cm 2time engraving matrix depth value be recorded in lower Table I.This presoma is extremely hard, does not show elastomer properties.In addition, in the flexographic printing component of laser ablation, serious melted edge is observed in the edge of feature.
Comparative example 2:
By styrene-butadiene triblock copolymer TPE (4.7g, Kraton Dl102K, there is 28% polystyrene content, from Kraton Polymers LLC, Houston, TX) with carbon black powders (0.3g, Mogul L, from Cabot Corp Boston, MA) combination and in ThermoHaake double screw extruder (model MiniLab Rheomix CTW5) at 190 DEG C 60rpm melting mixing 5 minutes, go out extruder, and make it cool.This produces the Kraton of 94 % by weight and the carbon black of 6 % by weight.Sample (3.5g) melting of this mixture being molded to be formed can the layer of laser engraving, using 5.3 watts, the single mode ytterbium fibre laser of 1064nm pulse carries out laser engraving, as described in inventive embodiments 1, standing swelling test.Laser flux is 102J/cm 2time engraving the depth value of matrix be recorded in lower Table I.Kraton is for non-nano crystallization TPE and the result shown in Table I shows that this presoma demonstrates the solvent swell of unacceptable level.
Comparative example 3:
Use ultra-violet radiation, under back and face exposure time and energy, by commercially available flexographic printing plates presoma Flexcel NX (Eastman Kodak Company, thickness 2.7mm) evenly exposure (imaging) is crosslinked to lure, and use the treatment conditions of recommending in product description to carry out processing (development).Remove PET supporter from the flexographic printing plates of gained, and repeat rheology test mentioned above.The G ' of this material and G " frequency response of modulus is shown in Figure 1.
Comparative example 4:
The rubber flexible lithographic printing plate presoma (Bottcher Flex 787, thickness 1.7mm) of commercially available sulfuration is obtained from Bottcher Systems (Germany).Remove PET supporter from precursor samples, and repeat the test of above-described rheology.The G ' of this presoma and G " frequency response of modulus is shown in Figure 1.
Fig. 1 shows, for the presoma of inventive embodiments 2, when drawing with log-log form, be respectively G ' and the G of energy storage modulus and loss modulus value "; reduce continuously with the reduction of frequency of oscillation in stub area; have close to or higher than 1 slope, show that the presoma of the embodiment of the present invention 2 is melt-processable.On the other hand, for the presoma of the chemical crosslinking of comparative example 3 and 4, G ' and G " modulus approaches zero slope when frequency of oscillation changes, and shows that they are crosslinked and non-melt processing, as defined in the present invention.
Table I
Presoma embodiment Adhesive Adhesive-carbon black ratio 102 J/cm 2The spot degree of depth under flux Swelling % in IPA/EA 8/2 after 24 hours Elasticity
Invention 1 Notio?PN-2060 94/6 240 5.8 Well
Invention 2 Notio?PN-2060 93/7 236 5.8 Well
Invention 3 Notio?PN-0040 93/7 258 5.0 Well
Invention 4 Notio?PN-20300 93/7 245 5.1 Well
Invention 5 Notio?PN-2070 93/7 224 5.7 Well
Invention 6 Notio?PN-3560 93/7 258 5.9 Well
Invention 7 Engage? 8200 93/7 192 3.3 Well
Invention 8 Engage? 8401 93/7 181 2.4 Well
Contrast 1 Polypropylene 93/7 207 0.5 Difference
Contrast 2 KratonD1102K 94/6 227 15.0 Well
Result shown in Table I confirms, when nanocrystal polyolefin flexographic printing plates presoma can be used as adhesive in the layer of laser engraving time, realize the combination of advantageous property of high-quality laser ablation imaging, low solvent swell and favorable elasticity.When be used as containing cinnamic non-nano crystalline polyolefin or noncrystalline TPE can adhesive in the layer of laser engraving time, the character of gained is not desirable.
Inventive embodiments 9:
By at this blender of Bradley (ATR-2120, be configured with 3 thermals treatment zone and high shear drum-type blade) at 220 DEG C 45 rpm melting mixing 10 minutes, by nanocrystal polyolefin grain (30.7g, Notio PN-20300, from Mitsui Chemicals America company, Rye Brook, NY) and carbon black powders (2.9g, Mogul ?l, from Cabot Corp Boston, MA) and calcium carbonate (CaCO 3, 8.4g, Multiflex MM, from Specialty Minerals Bethlehem, PA) and combination, remove and make it cool.This produce the Notio PN-20300 of 73 % by weight, the carbon black of 7 % by weight and 20 % by weight calcium carbonate.Sample (3.5g) melting of gained mixture is molded as flexographic printing plates presoma of the present invention, and as described in inventive embodiments 1, uses 5.3 watts, the single mode ytterbium fibre laser laser engraving of 1064nm pulse.Laser flux is 102 J/cm 2time engraving matrix depth value be recorded in lower Table II.
Inventive embodiments 10-14:
The flexographic printing plates presoma of the present invention with laser engraving is prepared, except combining different nanocrystal polyolefin and different inorganic fillers, shown in following Table II as described in inventive embodiments 9.Barium sulfate (BaSO 4, Sachtosperse HU-D, from Sachtleben Chemie Postfach, Duisburg Germany), talcum (Ultratalc ?609, from Specialty Minerals Barretts, MT), calcium sulfate (CaSO 4, Drierite, from W.A. Hammond Drierite Co. Xenia, OH).Laser flux is 102J/cm 2time engraving the depth value of matrix be recorded in lower Table II.
Manually flex samples, the interpolation observing inorganic additive adds the rigidity of material.
Table II
Presoma embodiment Adhesive Inorganic additive At 102 J/cm 2The spot degree of depth under flux
Invention 9 Notio? PN-20300 CaCO 3 200
Invention 10 Notio? PN-20300 BaSO 4 221
Invention 11 Notio? PN-20300 Talcum 197
Invention 12 Notio? PN-2060 CaSO 4 163
Invention 13 Notio? PN-2060 Talcum 188
Result shown in Table II confirms, in the layer of laser engraving, nanocrystal polyolefin as herein described and various inorganic filler can combined, with provide can the flexographic printing plates presoma of laser engraving and the flexographic printing plates of imaging physical property change and still maintain high-quality laser engraving character.
Inventive embodiments 14:
By at this blender of Bradley (ATR-2120, be configured with 3 thermals treatment zone and high shear drum-type blade) at 220 DEG C 45 rpm melting mixing 10 minutes by nanocrystal polyolefin grain (33.5g, Notio PN-2060, from Mitsui Chemicals America company, Rye Brook, NY) with carbon black powders (3.2g, Mogul L, from Cabot Corp Boston, MA) and polypropylene (8.4g, CAS 25085-53-4, from Sigma-Aldrich St. Louis, MO) combine, remove and make it cool.This produces the Notio PN-2060 of 74.4 % by weight, the carbon black of 7 % by weight, and the polypropylene of 18.6 % by weight.Sample (3.5g) melting of gained mixture being molded as flexographic printing plates presoma of the present invention, and as described in inventive embodiments 1, using 5.3 watts, the single mode ytterbium fibre laser of 1064nm pulse carries out laser engraving.When laser flux is 102J/cm 2time engraving matrix depth value be recorded in lower Table III.
Inventive embodiments 15:
As described in inventive embodiments 14, preparation and laser engraving flexographic printing plates presoma of the present invention, substitute polypropylene except using polyolefin elastomer (Engage 8200, Dow Chemical Ayer, MA).When laser flux is 102J/cm 2time, the matrix depth value of engraving is recorded in lower Table III.
Table III
Presoma embodiment Adhesive component 1 Adhesive component 2 102 J/cm 2The spot degree of depth under flux
Invention 14 Notio? PN-2060 Polypropylene 247
Invention 15 Notio? PN-2060 Engage? 8200 251
Result shown in Table III confirms, nanocrystal polyolefin can with other combination of polymers, other polymer described can provide can the change of physical property (such as hardness) of the layer of laser engraving and the image forming of gained, and still keeps high-quality laser ablation imaging character.The Shore A hardness number of Notio PN-2060 is 82, and is 66 (ASTM D2240) for Engage 8200.Polyacrylic Shore D hardness number scope is 70-80 (polymer handbook, the third edition, J. Brandrup and E.H. Immergut, editor, John Wiley & Sons, NY, 1989).
Inventive embodiments 16:
By at this blender of Bradley (ATR-2120, be configured with 3 thermals treatment zone and high shear drum-type blade) in 220 DEG C and under 45 rpm meltings, mix 10 minutes by nanocrystal polyolefin grain (38.0g, Notio PN-2060, from Mitsui Chemicals America company, Rye Brook, NY) with xGnP M-5 graphene powder (2.9g, exfoliated graphene nano particle, from XG Sciences, East Lansing, MI) combine, remove and make it cool.This produces the Notio PN-2070 of 93 % by weight and the Graphene of 7 % by weight.Sample (3.5g) melting of this gained mixture being molded as flexographic printing plates presoma of the present invention, and as described in inventive embodiments 1, using 5.3 watts, the single mode ytterbium fibre laser of 1064nm pulse carries out laser engraving.Laser flux is 102J/cm 2time engraving matrix depth value be 245 μm.
Inventive embodiments 17:
By thermoplastic elastomer (TPE) nanocrystal polyolefin grain (42.0g, Notio PN-2060, from Mitsui Chemicals America company, Rye Brook, NY) and carbon black powders (3.2g, Mogul L, from Cabot Corp Boston, MA) combination and at this blender of Bradley (ATR-2120 is configured with 3 thermals treatment zone and high shear drum-type blade) 200 DEG C and 45rpm melting mixing 10 minutes, remove and make it cool.This produce there is the Notio PN-2060 of 93 % by weight and the carbon black of 7 % by weight can the layer composition of laser engraving.The sample (3.5g) of this mixture is incorporated into side there is 300FN Kapton so that release aluminum dipping form in, and use the Carver press (model #_3393) be set at 20 MPas and 220 DEG C through 5 minutes, this sample to be pressed into the shape of flat article.Then be cold pressing the module sets of mould and its content 30 minutes in another Carver press of not heating of 20 MPa.The of the present invention of gained can the flexographic printing plates presoma size of laser engraving be that 75 × 75mm and about 0.8mm are thick.
As described in inventive embodiments 1, using 5.3 watts, this version presoma of laser engraving can carry out laser engraving by the single mode ytterbium fibre laser of 1064nm pulse.Laser flux is 102J/cm 2time engraving matrix depth value be 233 μm.
How the flexographic printing plates of engraving can be reclaimed to demonstrate, being cut into the block of 5-10 mm size subsequently with scissors.These blocks are weighed and above-describedly can the layer composition of laser engraving add in these blocks by extra, until gross weight is for filling 3.5 grams needed for mould, and be added to and there is 300FN Kapton so that in the aluminum dipping form of release in side, and use and be set as that the shape that 5 minutes become flat article suppressed by the Carver press (model #_3393) of 20 MPas and 220 DEG C.Then the assembly of mould and its content is being set as colding pressing 30 minutes in another Carver press that 20 MPa do not heat.Gained can the size of flexographic printing plates presoma of laser engraving be that 75 × 75mm and about 0.8mm are thick.Use laser instrument identical described above, this making to be formed by salvage material can the version presoma imaging of laser engraving.Laser flux is 102J/cm 2time engraving matrix depth value be 228 μm.
Describe the present invention in detail with particular reference to some preferred embodiment of the present invention, but should understand and can carry out within the spirit and scope of the present invention changing and changing.

Claims (14)

1. can the flexographic printing presoma of laser engraving for what provide matrix, described presoma comprise at least one elastomeric, formed embossment, non-chemically crosslinked, can the layer of laser engraving, described layer comprises the nanocrystal polyolefin of thermoplastic elastomer (TPE), wherein said elastomeric, formed embossment, non-chemically crosslinked, the layer of laser engraving can comprise the chemical cross-linking agent being less than 0.1 % by weight.
2. according to claim 1 can the flexographic printing presoma of laser engraving, wherein said elastomeric formation embossment, non-chemically crosslinked, can the layer of laser engraving there is G ' and G " modulus; logarithm draw time; higher than described can laser engraving layer fusion temperature temperature under, described G ' and G " modulus reduces continuously along with the reduction of frequency of oscillation.
3. according to claim 1 and 2 can the flexographic printing presoma of laser engraving, wherein said elastomeric, formed embossment, non-chemically crosslinked, can the layer packet content of laser engraving be at least 30 % by weight and at the most and comprise the nanocrystal polyolefin of the described thermoplastic elastomer (TPE) of 100 % by weight.
4. according to any one of claim 1 to 2 can the flexographic printing presoma of laser engraving, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin has the glass transition temperature being less than or equal to 10 DEG C.
5. according to any one of claim 1 to 2 can the flexographic printing presoma of laser engraving, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin is selected from substantially by the group of the following polymer formed: the polyolefin comprising at least propylene recurring units, comprise the polyolefin of ethylene repeating unit and octene repetitive, comprise the polyolefin of ethylene repeating unit and propylene recurring units, and comprise the polyolefin of ethylene repeating unit, propylene recurring units and butene repeat unit.
6. according to any one of claim 1 to 2 can the flexographic printing presoma of laser engraving, wherein said elastomeric, formed embossment, non-chemically crosslinked, the layer of laser engraving can go back the radiation adsorber that packet content is at least 0.5 % by weight.
7. according to any one of claim 1 to 2 can the flexographic printing presoma of laser engraving, wherein said elastomeric, formed embossment, non-chemically crosslinked, the layer of laser engraving can go back chemical non-activity particle or the microcapsules that packet content is at least 2 % by weight.
8. can form the material of image, its comprise elastomeric, form embossment, non-chemically crosslinked, can laser engraving, the polyolefinic layer of nanocrystal containing thermoplastic elastomer (TPE), and the radiation adsorber in identical or different layer.
9. the material forming image according to claim 8, wherein said thermoplastic elastomer (TPE) nanocrystal polyolefin and radiation adsorber identical elastomeric, formed embossment, non-chemically crosslinked, can in the layer of laser engraving, and described nanocrystal polyolefin with at least 30 % by weight and at the most and the amount comprising 98 % by weight be present in described elastomeric, formed embossment, be non-chemically cross-linked, can in the layer of laser engraving.
10. the material of formed image according to claim 8 or claim 9, wherein said radiation adsorber is absorber of infrared radiation.
11. for maybe can form image at flexographic printing component material in the method for matrix is provided by laser engraving, it comprises and the flexographic printing presoma of laser engraving maybe will can form the material Imagewise exposure of image in laser engraving radiation, to provide the component of the flexographic printing with matrix according to any one of claim 1 or 8.
12. methods according to claim 11, it provides the flexographic printing component or figuratum material with matrix, and described matrix has at least 50 and at the most and comprise the maximum dry degree of depth of 1000 μm.
The method of 13. flexographic printings, it comprises:
By according to any one of claim 1 to 2 can the flexographic printing presoma Imagewise exposure of laser engraving in laser engraving radiation, to provide the component of the flexographic printing with matrix, and
Use described flexographic printing component in flexographic printing.
14. for laser engraving flexographic printing plates presoma to form the system of flexographic printing component, described system comprises:
Any one of claim 1 to 2 can the flexographic printing presoma of laser engraving, and
One or more laser engraving radiation source, its be directed to provide described elastomeric, formed embossment, non-chemically crosslinked, can the laser engraving of layer of laser engraving.
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